ABSTRACT
Samples of magnesium aluminum spinel ceramics doped with manganese ions were prepared by a high-temperature solid-state reaction method; their potential as red-emitting phosphors was analyzed using a time-resolved luminescence spectroscopy technique, from room temperature to 10 K. It was found that in the red spectral range, the luminescence spectra of manganese ions in the MgAl2O4 spinel showed a narrow band peaking at 651 nm due to the emission of Mn4+ and a broader emission band in the region of 675 ÷ 720 nm; the ratio of intensities for these bands depends on the synthesis conditions. By applying a special multi-step annealing procedure, the MgAl2O4:Mn4+ phosphor containing only tetravalent manganese ions, Mn4+, was synthesized. Broad-band far-red emission observed from MgAl2O4:Mn and Mg1.25Al1.75O3.75F0.25:Mn phosphors, prepared by a conventional method of a solid-state reaction, was interpreted as coming from Mn3+ ions.
ABSTRACT
The low-temperature absorption and excitation spectra of interconfigurational 4f-5d transitions of Tb(3+) in a cubic fluoride host demonstrate the appearance of a first-order linear Jahn-Teller effect for the high-spin excited states of the excited electronic configuration 4f(7)5d involving 5d t(2g) orbitals. The τ(2g) mode is observed to be responsible for the splitting of the otherwise degenerate 5d t(2g) orbitals.
Subject(s)
Lanthanoid Series Elements/chemistry , Circular Dichroism , Cold Temperature , Crystallization , Electron Spin Resonance Spectroscopy , Electrons , Quantum TheoryABSTRACT
The emission and excitation spectra of Ce(3+) and Pr(3+) doped into the cubic host Cs(2)NaYF(6) have been recorded at room temperature and â¼10 K using synchrotron radiation. The two 5d(1) T(2g) states of Ce(3+) have been located from the excitation spectra, whereas the E(g) state is placed above the host band gap. Decay measurements of the 5d(1) â 4f(1) Ce(3+) emission, and spectra collected using selective excitation, indicate the occupation of more than one type of site by Ce(3+) in this host lattice. By contrast, the location of features in the 4f(1)5d(1) â 4f(2) emission of Pr(3+) is independent of the excitation wavelength. Assignments are presented for some of the 4f(1)5d(1) levels and for the Pr(3+)-F(-) charge transfer band. The 5d emission lifetimes for Ce(3+) and Pr(3+) in the Cs(2)NaYF(6) host are 42 and 29 ± 1 ns, respectively, and are not temperature-dependent.
ABSTRACT
Vacuum ultraviolet excitation spectra at â¼10 K have been recorded for [Formula: see text] transitions of Cs(2)NaYF(6):Ln(3+) (Ln = Nd, Sm, Eu, Tb, Ho, Er, Tm). In these high bandgap hosts the lanthanide ions occupy octahedral symmetry sites. The spectra comprise broad, structured bands and in most cases the individual vibronic structure is not resolved. Simulations of the relative intensities and band positions in the spectra have been made by using parameter values from previous studies and/or by employing values from similar systems or estimating trends across the lanthanide series, without data fitting or parameter adjustments. The agreement with experimental results is reasonable except where the luminescent state being monitored is not efficiently populated nonradiatively from the 4f(N-1)5d state, or where additional bands are present. The latter are readily assigned to charge transfer transitions or the near-excitonic band. Comparison of the spectra has been made with those of other high symmetry lanthanide ion systems.
ABSTRACT
Excitation of the 4f3 ion Nd3+ in hexafluoroelpasolite lattices by synchrotron radiation of wavelength approximately 185 nm leads to fast 4f(2)5d --> 4f3 emission below 52,630 cm(-1) and slower 4f3 --> 4f3 emission from the luminescent states (4)F(3/2) gamma8u (11 524 cm(-1)) and 2G2(9/2) gamma8u (approximately 47,500 cm(-1)). The near-infrared emission is well-resolved, and a clear interpretation of the 4I(9/2) crystal field levels and of the one-phonon vibronic sideband is given. The excitation spectrum of the 2G2(9/2) emission enables clarification of the structure of the 4f(2)5d configuration (which extends from approximately 52,000 to 128,000 cm(-1)). Detailed energy level and intensity calculations have been performed, which provide simulations of the d-f emission and the f-d excitation spectra in good agreement with experiment. It is interesting that although the 4f3 2G2(9/2) gamma8u --> 4f3 4I(J) transitions are very weak in intensity compared with transitions terminating upon higher multiplet terms, most of the 4f(2)5d (3H) 4I(9/2) gamma8g --> 4f3 emission intensity resides in the transitions to 4I(J).
